EP1422782B1 - Photoelectric conversion element sensitized with methine dyes - Google Patents

Photoelectric conversion element sensitized with methine dyes Download PDF

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Publication number
EP1422782B1
EP1422782B1 EP02745855A EP02745855A EP1422782B1 EP 1422782 B1 EP1422782 B1 EP 1422782B1 EP 02745855 A EP02745855 A EP 02745855A EP 02745855 A EP02745855 A EP 02745855A EP 1422782 B1 EP1422782 B1 EP 1422782B1
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Prior art keywords
group
optionally substituted
photoelectric conversion
hydrocarbon residue
conversion device
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German (de)
English (en)
French (fr)
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EP1422782A4 (en
EP1422782A1 (en
Inventor
Masaaki Nippon Kayaku K.K. IKEDA
Koichiro Nippon Kayaku K.K. SHIGAKI
Teruhisa Nippon Kayaku K.K. INOUE
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority claimed from JP2001247963A external-priority patent/JP5051810B2/ja
Priority claimed from JP2001308382A external-priority patent/JP4005330B2/ja
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Priority to EP10178386A priority Critical patent/EP2259378A1/en
Priority to EP10178494.0A priority patent/EP2262050B1/en
Publication of EP1422782A1 publication Critical patent/EP1422782A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B56/00—Azo dyes containing other chromophoric systems
    • C09B56/16—Methine- or polymethine-azo dyes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0075—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0091—Methine or polymethine dyes, e.g. cyanine dyes having only one heterocyclic ring at one end of the methine chain, e.g. hemicyamines, hemioxonol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0805—Amino benzenes free of acid groups
    • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C09B29/081—Amino benzenes free of acid groups characterised by the amino group substituted amino group unsubstituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino, aralkylamino or arylamino
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C09B55/002—Monoazomethine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B56/00—Azo dyes containing other chromophoric systems
    • C09B56/08—Styryl-azo dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/652—Cyanine dyes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a semiconductor fine material sensitized with an organic dye, a photoelectric conversion device and a solar cell, and in particular to an oxide semiconductor fine material sensitized with a dye having a specific structure, a photoelectric conversion device characterized by using the oxide semiconductor fine material and a solar cell using the photoelectric conversion device.
  • a solar cell utilizing sunlight as an alternative energy source to a fossil fuel such as petroleum, coal or the like has been paid attention to.
  • Efficiency-enhancement studies have been conducted enthusiastically nowadays for the development and improvement of a silicon solar cell wherein used crystalline or amorphous silicon; or a compound semiconductor solar cell wherein used gallium, arsenic or the like.
  • they have not widely been accepted in the market because of the high production cost and energy-consumption as well as the difficulties relating to the resources problem. Due to the above, the development of cost-effective solar cells has been desired.
  • a photoelectric conversion device comprising semiconductor fine particles sensitized with dye(s) and a solar cell comprising said photoelectric conversion device have been known, whereupon disclosed material and techniques for producing the same.
  • the present inventors have conducted an extensive study in order to solve the above-described problems and found that a photoelectric conversion device having high conversion efficiency can be obtained by sensitizing semiconductor fine materials with a dye having the specific partial structure and preparing a photoelectric conversion device.
  • the present invention has thus been completed based on those findings.
  • the present invention relates to;
  • a photoelectric conversion device uses an oxide semiconductor sensitized with a dye having a specific partial structure, particularly an oxide semiconductor fine material.
  • a dye having a specific partial structure particularly an oxide semiconductor fine material.
  • the oxide semiconductor fine material used in the present invention which may be the oxide semiconductor fine particle or the fine crystalline such as nanowhisker, nanotube and nanowire as far as the surface area thereof is large enough to adsorb much dye; preferably adsorb as much dye or even more dye than the oxide semiconductor fine particle.
  • the oxide semiconductor fine particle is most commonly used.
  • Each dye of the present invention, having a specific partial structure is namely characterized by comprising respectively methine groups and being represented by the following formula (10): wherein,
  • aliphatic hydrocarbon residue includes a residue group obtained by removing one hydrogen atom from both straight and branched - chain or cyclic aliphatic hydrocarbon, which may be saturated and unsaturated and it generally has from 1 to 36 carbon atoms, although the number of carbon atoms are not particularly limited.
  • Preferred is an alkyl group of straight-chain having from 1 to about 20 carbon atoms, and most commonly is an alkyl group of straight-chain having from 1 to about 6 carbon atoms.
  • Example of a cyclic aliphatic hydrocarbon residue includes a cycloalkyl group having 3 to 8 carbons.
  • aromatic hydrocarbon residue means a group wherein one hydrogen atom is removed from an aromatic hydrocarbon such as benzene, naphtalene, anthracene, phenanthrene, pyrene, indene, azulene and fluoren.
  • heterocyclic residue means a group wherein one hydrogen atom is removed from a heterocyclic compound such as pyridine, pyrazine, piperidine, morpholine, indoline, thiophene, furan, oxazole, thiazole, indole, benzothiazole, benzoxazole and quinoline.
  • optionally substituted amino group include an unsubstituted amino group, optionally substituted mono- or dialkylamino group and mono- or diaromatic substituted amino group such as mono- or dimethylamino group, mono- ordiethylamino group, mono- or dipropylamino group, mono- or dibenzylamino group, mono- or diphenylamino group, mono- or dinaphtylamino group and alkylarylamino group (examples of substituents on an alkyl group and an aryl group include, but are not limited to, a phenyl group, an alkoxyl group, a halogen atom, a hydroxyl group and a cyano group).
  • alkoxyl group examples include an alkoxyl group having 1 to 10 carbon atoms.
  • halogen atom examples include chlorine, bromine and iodine.
  • alkoxycarbonyl group examples include an alkoxycarbonyl group having 1 to 10 carbon(s).
  • acyl group examples include a C 1-10 alkylcarbonyl group and an arylcarbonyl group, preferably is a C 1-4 alkylcarbonyl group, and more specifically are an acetyl group and a propionyl group.
  • substituted or unsbstitutedmercapto group a substituted or unsbstituted amino group, a substituted or unsbstituted amide group, an alkoxyl group, an alkoxyalkyl group or a substituted carbonyl group such as a carboxyl group, a carbonamide group, an alkoxycarbonyl group and an acyl group.
  • optionally substituted alkyl group generally include both straight and branched -chain or cyclic alkyl group being optionally substituted, having from 1 to 36 carbon atoms, and preferably an alkyl group having from 1 to about 20 carbon atoms. Most commonly is an optionally substituted alkyl group having from 1 to about 6 carbon atoms.
  • the alkyl group may further be substituted with the substituents excluding the above alkyl group.
  • aryl group examples include a group wherein a hydrogen atom is removed from an aromatic ring of the above mentioned aromatic hydrocarbon residue.
  • the aryl groups may further be substituted with the above-described groups.
  • halogen atom examples include an atom such as fluorine, chlorine, bromine and iodine.
  • phosphoric acid ester group examples include an (C 1 -C 4 )alkyl phosphoric acid ester group.
  • unsubstituted or substituted mercapto group examples include such as a mercapto group and an alkylmercapto group.
  • unsubstituted or substituted amino group examples include such as an amino group, mono- or dialkylamino group, mono- or diaromatic group, mono- or dimethylamino group, mono-or diethylamino group, mono- or dipropylamino group, mono- or diphenyl amino group or a benzylamino group.
  • substituted or unsubstituted amide group examples include such as an amide group, an alkylamide group and an aromatic amide group.
  • Amide group referred in the specification may be either a sulfone amide group or a carbonamide group, but generally means a carbonamide group.
  • alkoxy group examples include such as an alkoxyl group having from 1 to 10 carbon atoms.
  • alkoxyalkyl group examples include such as a (C 1 -C 10 )alkoxy(C 1 -C 10 )alkyl group.
  • alkoxycarbonyl group examples include such as an alkoxycarbonyl group having from 1 to 10 carbon atoms.
  • acryl group examples include such as an alkyl carbonyl group having from 1 to 10 carbon atoms, an aryl carbonyl group, preferably is an alkyl carbonyl group having from 1 to 4 carbon atoms, and specifically are such as an acetyl group and a propionyl group, etc..
  • Acid group such as carboxyl group, sulfo group and phospholic acid group, and "hydroxyl group” may form salts.
  • salts include the salts formed with alkaline metals or alkaline earth metals such as lithium, sodium, potassium, magnesium and calcium; or the salts such as quaternary ammonium salts, e.g. tetramethylammonium, tetrabutylammonium, pyridinium and imidazolium, formed with organic base.
  • Preferred A1, A2 and A3 include a hydrogen atom, a halogen atom, a cyano group, an amino group which may be optionally substituted by alkyl group having 1-4 carbon atoms or phenyl group, an optionally substituted alkyl group and an optionally substituted phenyl group, and more preferably are a hydrogen atom or an optionally substituted (C 1 -C 4 ) alkyl group.
  • any two among A1, A2 and A3 may be bonded to form an optionally substituted ring.
  • n is 2 or more and A1 or A2, or both A1 and A2 present in plural, any A1 and any A2 may be combined to form a ring.
  • the substituents include those mentioned for the aliphatic hydrocarbon residue, aromatic hydrocarbon residue or heterocycle residue described above.
  • the formed-rings are unsaturated hydrocarbon rings and heterocycle rings.
  • unsaturated hydrocarbon rings include such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, indene ring, azulene ring, fluorene ring, cyclobutene ring, cyclohexene ring, cyclopentene ring, cyclohexadiene ring and cyclopentadiene ring.
  • heterocycle rings include such as pyridine ring, pyrazine ring, indoline ring, thiophene ring, furan ring, pyran ring, oxazole ring, thiazole ring, indole ring, benzothiazole ring, benzoxazole ring, pyrazine ring, quinoline ring, carbazole ring and benzopyran ring.
  • the ring may also be a condensed ring such as benzothiazole.
  • Examples of those include such as a cyclobutene ring, cyclopentene ring, cyclohexene ring and pyran ring. Those may have substituents such as carbonyl group and thiocarbonyl group, and in such a case may form a cyclic ketone or a cyclic thioketone.
  • X1 represents an oxygen atom, a sulphur atom, a selenium atom or -NR"- (wherein R" represents a hydrogen atom or an optionally substituted aliphatic hydrocarbon residue, an optionally substituted aromatic hydrocarbon residue, an optionally substituted heterocyclic residue), preferably are an oxygen atom and a sulphur atom, and more preferably is an oxygen atom.
  • R" represents a hydrogen atom or an optionally substituted aliphatic hydrocarbon residue, an optionally substituted aromatic hydrocarbon residue, an optionally substituted heterocyclic residue
  • R" represents a hydrogen atom or an optionally substituted aliphatic hydrocarbon residue, an optionally substituted aromatic hydrocarbon residue, an optionally substituted heterocyclic residue
  • Y1 is represented by the following general formula (11): wherein,
  • alkyl group and alkoxyl group herein referred are the same as those mentioned for A1, A2 and A3.
  • R11 and R12 may be bonded to form an optionally substituted ring, R11 and R12 may independently be combined with R13 to form a julolidine ring, tetramehtyl julolidine ring, a quinoline ring and a carbazole ring.
  • Preferred groups in R11 and R12 include an unsubstituted alkyl group having from 1 to 8 carbon atoms, more preferably having from 1 to 5 carbon atoms; or said alkyl group having a substituent selected from the group consisting of a cyano group, a hydroxy group, a halogen atom, a phenyl group, a (C 1 -C 4 )alkyl substituted phenyl group, an (C 1 -C 4 )alkoxyl group, an (C 1 -C 4 )acyl group and phenoxy group.
  • R1 represents a hydrogen atom, a cyano group, an optionally substituted aliphatic hydrocarbon residue, an optionally substituted aromatic hydrocarbon residue, an optionally substituted heterocyclic residue or a substituted-carbonyl group such as carboxyl group, a carbon amide group, an alkoxyl carbonyl group and acyl group.
  • the optionally substituted aliphatic hydrocarbon residue, the optionally substituted aromatic hydrocarbon residue and the optionally substituted heterocyclic residue are the same as those mentioned for A1, A2 and A3.
  • Preferred groups for R1 may include a cyano group, an optionally substituted aliphatic hydrocarbon residue; more preferably are (C 1 -C 4 )alkyl group or a substituted-carbonyl group such as a carboxyl group, a carbonamide group, an alkoxycarbonyl group and an acyl group; and further preferably are a carboxyl group, (C 1 -C 4 )alkoxycarbonyl group, a carboxyamide group optionally substituted with N-(C 1 -C 4 )alkyl group, C1-C6 acyl group and cyano group; most preferably is a carboxyl group.
  • R2 represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon residue, an optionally substituted aromatic hydrocarbon residue or optionally substituted heterocyclic residue. Examples of those are the same as mentioned for A1, A2 and A3.
  • Preferred substituents for those groups include the groups having an alkyl group, an aryl group, a cyano group, a nitro group, a halogen atom, a hydroxyl group, a sulfo group, a phosphoric acid group, a phosphoric acid ester group, a substituted or unsubstituted amino group, an alkoxyl group, an alkoxyalkyl group, a group having a carbonyl group such as a substituted or unsubstituted amide group, a carboxyl group, an alkoxycarbonyl group and an acyl group, and more preferably are a cyano group, a halogen atom, a carboxyl group, a (C 1 -C 4
  • Preferred R2 represents an unsubstituted phenyl group; a phenyl group having from 1 to 3 substituents selected from the group consisting of (C 1 -C 4 )alkyl group, a sulfo group and a halogen atom; an unsubstituted (C 1 -C 4 )alkyl group; a (C 1 -C 4 )alkyl group having substituents selected from the group consisting of carboxyl group, halogen atom and hydroxyl group; a 5-membered aliphatic hydrocarbon residue optionally having from 1 to 2 oxygen atoms or sulphur atoms.
  • R1, R2 and X1 are preferred to have a carbonyl group such as carboxyl group, a carbonamide group, alkoxycarbonyl group and acyl group in order to form an adsorption bond with the oxide semiconductor.
  • n1 represents an integer from 0 to 4.
  • n1 is an integer from 0 to 3, and more preferably from 0 to 2.
  • the preferred compound represented by the formula (10) is a compound having a combination of the above preferred groups. More preferably is a compound wherein R1 is carboxyl group, R2 is an unsubstituted phenyl group and X1 is an oxygen atom, A1, A2 and A3 are hydrogen atoms, n1 is an integer from 0 to 2, Y1 is a group represented by the formula (11). Further preferably, in the general formula (11), R11 and R12 are (C 1 -C 4 )alkyl groups, and R13 is an hydrogen atom.
  • the compound represented by the general formula (10) may include the structural isomers such as cis form and trans form, and either of them may be used as a photosensitizing dye without any limitation.
  • the compound represented by the general formula (10) can be synthesized by condensing a pyrazoron derivative represented by the general formula (20) with a carbonyl derivative represented by the general formula (21) in the aprotic polar solvents such as alcohol (methanol, ethanol and isopropanol, etc.) and dimethylformamide, or acetic anhydride at 20°C to 120°C, preferably at about 50°C to 80°C, if necessary, in the presence of a basic catalyst such as sodium ethoxide, piperidine and piperazine.
  • aprotic polar solvents such as alcohol (methanol, ethanol and isopropanol, etc.) and dimethylformamide, or acetic anhydride at 20°C to 120°C, preferably at about 50°C to 80°C, if necessary, in the presence of a basic catalyst such as sodium ethoxide, piperidine and piperazine.
  • Examples of the compound are shown below.
  • Examples of the compound represented by the general formula (22) wherein each of A1, A2 and A3 in the general formula (10) is a hydrogen atom and Y1 is 4-aminobenzene derivative are shown in Table 1, wherein 4-sulfonbenzene group, phenyl group and naphtalene are respectively abbreviated as 4-SB, Ph and Np. The same abbreviation is applied to Table 2 unless otherwise stated.
  • a dye-sensitized photoelectric conversion device of the present invention for example, is produced by forming a thin film using the oxide semiconductor fine materials on the substrate, and subsequently a dye being adsorbed thereon.
  • Preferred substrate of the present invention to form the oxide semiconductor thin film thereon has an electrically conductive surface, which is available in the market. More specifically preferred is the substrate wherein a thin film of electrically conductive metal oxide such as tin oxide being doped with indium, fluorine or antimony or thin film of metal such as gold, silver or copper is formed on the surface of glass or a transparent high-molecular material such as polyethylene terephthalate or polyether sulfone.
  • the sufficient conductivity thereof is usually 1,000 ⁇ or less, and is preferably 100 ⁇ or less.
  • oxide semiconductor fine materials particularly for oxide semiconductor fine particles, metal oxides are preferable.
  • oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, vanadium and the like preferably include oxides of titanium, tin, zinc, niobium, tungsten and the like, and most preferably include oxides of titanium.
  • the oxide semiconductors may be used either alone or mixed.
  • An average particle diameter of the fine particles of the oxide semiconductor is generally from 1 nm to 500 nm, and preferably is from 5 nm to 100 nm. The larger particles and the smaller particles may be used by mixing together.
  • the oxide semiconductor fine crystaline such as nanowhisker, nanotube and nanowire may also be used.
  • An oxide semiconductor thin film can be produced by those methods such that the oxide semiconductor fine particles are directly vapor-deposited on a substrate to form a thin film; an oxide semiconductor thin film is electrically precipitated by using a substrate as an electrode; or a slurry of semiconductor fine particles is applied on a substrate, and then dried, cured or sintered to form a thin film.
  • the preferred is the method of using the slurry.
  • the slurry can be obtained by a conventional method wherein an oxide semiconductor fine particle of a secondary agglomeration state is dispersed in a dispersion medium as to form an oxide semiconductor fine particle of which average primary particle diameter is from 1 nm to 200 nm.
  • Any dispersion medium of the slurry can be used as far as it disperses the semiconductor fine particles.
  • Water or an organic solvent i.e. an alcohol such as ethanol; a ketone such as acetone, acetylacetone; or a hydrocarbon such as hexane and the mixture thereof may be used.
  • the use of water is preferable as to reduce the viscosity changes.
  • Sintering temperature of a slurry-coated substrate is generally 300°C or higher, preferably 400°C or higher.
  • the maximum allowable upper limit of sintering temperature thereof is approximately not greater than a melting point (softening point) of a substrate, generally is 900°C and preferably is 600°C or lower.
  • the total sintering time is preferably, but is not particularly limited to, within about 4 hours.
  • Thickness of the thin film on the substrate is generally from 1 ⁇ m to 200 ⁇ m, and preferably is from 5 ⁇ m to 50 ⁇ m.
  • the oxide semiconductor thin film may be subjected to a secondary treatment.
  • the thin film can directly be immersed together with the substrate in a solution of an alkoxide, a chloride, or a nitride, a sulfide or the like of the same metal as the semiconductor and then dried or sintered again to enhance performance of the semiconductor thin film.
  • metal alkoxides include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyl tin and the like, and an alcoholic solution thereof is used.
  • chlorides include titanium tetrachloride, tin tetrachloride, zinc chloride and the like, and an aqueous solution thereof is used.
  • a method to adsorb a dye on the oxide semiconductor thin film is explained.
  • a substrate on which the above-described oxide semiconductor thin film has been formed is immersed in a solution obtained by dissolving a dye in a solvent capable of dissolving the dye or in a dispersion liquid obtained by dispersing a dye with a low solubility.
  • a concentration of the dye dissolved in the solution or the dispersion liquid is determined depending on the dyes.
  • the semiconductor thin film formed on the substrate is immersed in the solution for about 1 to 48 hours at the temperature of the solvent from the normal temperature to boiling point.
  • solvents to be used for dissolving the dye include methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylformamide and the like.
  • a concentration of the dye in the solution is generally from 1x10 -6 M to 1 M, and preferably is from 1x10 -4 M to 1x10 -1 M. Consequently, a photoelectric conversion device of the oxide semiconductor thin film sensitized with the dye can be obtained.
  • the dye to be adsorbed may be composed of one type of die or the mixture of two or more types.
  • the dyes of the present invention may be mixed thereamong, or mixed with other dyes (including metal complex dyes) having no partial structure (1).
  • metal complex dyes for combined use include, but are not limited to, a ruthenium bipyridyl complex disclosed in J. Am. Chem. Soc., 115, 6382 (1993 ) or JP-A-2000-26487 , phthalocyanine, porphyrin and the like.
  • organic dyes for combined use include, dyes such as metal-free phthalocyanine, metal-free porphyrin, or methine-type dyes such as cyanine, merocyanine, oxonol, a triphenyl methane type, or a xanthene type, an azo type, an anthraquinone type and the like, and preferably include the ruthenium complex and methine-type dyes such as merocyanine.
  • a mixing ratio of the dyes is not particularly limited but is optimized depending on the respective dyes. However, the dyes are generally preferred to be mixed at from equivalent molar ratios to a ratio of about 10 mol% or more per dye.
  • a concentration of entire dyes in the solution may be the same as in the case of adsorbing only one type of dye.
  • an inclusion compound when adsorbing the dyes on the thin film of the oxide semiconductor fine particles.
  • the inclusion compounds include steroid-type compounds such as cholic acid, crown ethers, cyclodextrin, calixarene, polyethylene oxide, and preferably include cholic acid and polyethylene oxide.
  • a surface of a semiconductor electrode may be treated with an amine compound such as 4-t-butylpyridine.
  • the employed method for such a treatment is e.g. the method wherein a substrate having a thin film of the semiconductor fine particles on which the dye is adsorbed is immersed in an ethanol solution of an amine, or the like.
  • the solar cell of the present invention comprises a photoelectric conversion device electrode wherein the dye is adsorbed on the above-described oxide semiconductor thin film, a counter electrode and a redox electrolyte or a hole transfer material.
  • the redox electrolyte may be a solution wherein a redox pair is dissolved in a solvent, a gel electrolyte wherein a polymer matrix is impregnated with a redox pair or a solid electrolyte such as a fused salt.
  • hole transfer materials include an amine derivative, an electrically conductive polymer such as polyacetylene, polyaniline, polythiophene or the like, a material using a discotic liquid crystal phase such as polyphenylene and the like.
  • the preferred counter electrode to be used has electric conductivity and works as a catalyst duirng a reduction reaction of the redox electrolyte such as a glass or a polymer film on which platinum, carbon, rhodium, ruthenium or the like are vapor-deposited, or electrically conductive fine particles are applied.
  • Examples of redox electrolytes used in solar cells of the present invention include a halogen redox electrolyte comprising a halogen compound and halogen molecule having a halogen ion as a counter ion, a metal redox electrolyte of a metal complex or the like such as ferrocyanate-ferricyanate, ferrocene-ferricinium ion and an aromatic redox electrolyte such as alkylthiol-alkyldisulfide, a viologen dye, hydroquinone- quinone, and pref erably include the halogen redox electrolyte.
  • a halogen redox electrolyte comprising a halogen compound and halogen molecule having a halogen ion as a counter ion
  • a metal redox electrolyte of a metal complex or the like such as ferrocyanate-ferricyanate, ferrocene-ferricinium i
  • the halogen molecule in the halogen redox electrolyte comprising halogen compound - halogen molecule includes, for example, an iodine molecule, a bromine molecule or the like, and preferably includes the iodine molecule.
  • examples of the halogen compounds having a halogen ion as a counter ion include a halogenated metal salt such as LiI, NaI, KI, CsI and CaI 2 , or an organic quaternary ammonium salt of halogen such as tetraalkylammonium iodide, imidazolium iodide, pyridinium iodide, and preferably includes a salt-type compound having the iodine ion as a counter ion.
  • salt-type compounds having the iodine ion as a counter ion include lithium iodide, sodium iodide, a trimethyl iodide ammonium salt and the like.
  • the preferred solvent is an electrochemically inert solvent.
  • solvents include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, ⁇ -butyrolactone, dimethoxyethane, diethyl carbonate, diethyl ether, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxy ethane, dimethyl formamide, dimethyl sulfoxide, 1,3-dioxolane, methyl formate, 2-methyl tetrahydrofuran, 3-methoxy-oxaziridine-2-one, sulfolane, tetrahydrofuran, water and the like.
  • acetonitrile propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, 3-methoxyoxaziridine-2-one and the like.
  • solvents may be used either alone or in combination of two or more.
  • a polyacrylate or polymethacrylate resin, and the like are used as a matrix.
  • a concentration of the redox electrolyte is generally from 0.01% by weight to 99% by weight, and preferably from about 0.1% by weight to about 90% by weight.
  • the solar cell of the present invention can be obtained by allocating the counter electrode against an electrode of the photoelectric conversion device adsorbed the dye on the oxide semiconductor thin film on the substrate such that a sandwich of two electrodes and filling with a solution containing the redox electrolyte in between.
  • a dye was dissolved in ethanol in a concentration of 3 ⁇ 10 -4 M.
  • a porous substrate semiconductor thin film electrode prepared by the steps of: dispersing titanium dioxide P-25 available from Nippon Aerosil Co., Ltd. in an aqueous solution of nitric acid, applying the thus-dispersed titanium dioxide on a transparent electrically conductive glass electrode in a thickness of 50 ⁇ m; and sintering the resultant electrode at 450°C for 30 minutes
  • Example 1 one type of dye shown in Table 11 was used and adjusted to give the above-mentioned concentration, whereupon a photoelectric conversion device adsorbing the one type of dye was obtained by the above method.
  • Example 7 the solution was prepared by adjusting for two types of dyes as shown in Table 11 to give a concentration of 1.5 ⁇ 10 -4 M respectively, whereupon a photoelectric conversion device adsorbing the two types of dyes was obtained by the above method.
  • Examples 2, 5 and 6 one type of dye as shown in Table 11 was used and adjusted to give the above-mentioned concentration, whereupon a photoelectric conversion device adsorbing the one type of dye was obtained by the following method.
  • a 0.2 M aqueous solution of titanium tetrachloride was dropped onto an area of thin film of titanium oxide of the semiconductor thin film electrode, allowed to stand at room temperature for 24 hours, then washed with water and sintered at 450°C again for 30 minutes to give a semiconductor thin film electrode treated with titanium tetrachloride.
  • the dye was adsorbed thereon in the same manner as above using the resulting semiconductor thin film electrode.
  • one type of dye as shown in Table 11 was used and the above mentioned dye solution was prepared by adding cholic acid during adsorption procedure as an inclusion compound to give a concentration of 3 ⁇ 10 -2 M, then thus prepared dye solution was adsorbed on the semiconductor thin film to give a cholic acid-treated dye-sensitized semiconductor thin film.
  • Example 8 the solution was prepared by adjusting for two types of dye as shown in Table 11 to give a concentration of 1.5 ⁇ 10 -4 M respectively, and said two types of dye were adsorbed on the above mentioned semiconductor thin film treated with titanium tetrachloride to give a titanium tetrachloride - treated dye - sensitized semiconductor thin film.
  • the electrically conductive glass sheets of which surface was sputtered with platinum were fixed such that the above-prepared dye-sensitizing semiconductor thin film was interposed, then a solution containing an electrolyte (electrolyte solution) was poured into the gap. Two types of electrolyte solutions were prepared.
  • Example 7 an electrolyte solution A was used, which has been prepared by dissolving iodine, lithium iodide, 1,2-dimethyl-3-n-propyl imidazolium iodide, t-butyl pyridine in 3-methoxypropionitrile to give the concentrations of 0.1 M, 0.1 M, 0.6 M and 1 M, respectively.
  • Example 1-6 and 8 an electrolyte solution B was used, which has been prepared by dissolving iodine and tetra-n-propyl ammonium iodide in a solution of ethylene carbonate and acetonitrile (6:4) to give the concentrations of 0.02 M and 0.5 M respectively.
  • a size of a cell used for measurements was set such that an execution part thereof was 0.25 cm 2 .
  • a light source was set to be 100 mW/cm 2 through an AM 1.5 filter using a 500 W xenon lamp.
  • Short circuit current, open circuit voltage and conversion efficiency were measured by using a potentiogalvanostat.
  • a solar cell having high conversion efficiency as well as high stability has come to be provided by using a methine type dye having the specific partial structure. Further, by using the oxide semiconductor fine particles sensitized with two types of dye, the improvement in the conversion efficiency has been achieved.

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EP1422782A4 (en) 2007-05-02
EP2262050A1 (en) 2010-12-15
EP1422782A1 (en) 2004-05-26
EP2259378A1 (en) 2010-12-08
KR100864816B1 (ko) 2008-10-23
US20110031446A1 (en) 2011-02-10
US20110030801A1 (en) 2011-02-10
CA2453060C (en) 2011-02-08
CN1524315A (zh) 2004-08-25
CA2453060A1 (en) 2003-01-16
EP2262050B1 (en) 2013-09-04
DE60238922D1 (de) 2011-02-24
KR20040010840A (ko) 2004-01-31
US7851701B2 (en) 2010-12-14
AU2002318619B2 (en) 2007-09-13
CN1524315B (zh) 2013-02-13
US20040187918A1 (en) 2004-09-30

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